Condensation products having the constitution of acid amides and a process of preparing them



' Patented Sept. 10, 1940 UNITED sT TEs az acsi CONDENSATI nraonuc'rs HAVING PATENT omen THE CONSTITUTION OF'AGID AMIDES. AND A PROCESS PREPARING Karl Horst, Hofh'eim in hands, and Heinz Schild,

Frankfort-on-the-Main-Hochst, Germany, assignor's, by mesne assignments, to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application July 2a, 1938, Serial him-221,714. r ce aumtaiaa'z aliphatic hydrocarbon radicals whose carbon chain is interrupted by O, in the form of its anhydrlde o'r chloride to react with a compound of the general-formula 11-4 2. ELY

the group consisting of aliphatic, 'cycloaliphatic, aliphatic-aromatic and aromatic radicals, Ra

hydrogen, aliphatic, cycloaliphatic, aliphaticaromatic and aromatic hydrocarbon radicals, Y

stands for a member of the group consisting of OSOaMe and SOtMe, Mev being a member of the group consisting of alkali metals, NH; and the o radical NH4 in which at least one H atom and at most three H atoms are substituted. The amides thus obtained are of high capillary activity and may, therefore, be used as wetting, washing, purifying, dispersing and emulsi- 35 fylng agents.

Asaromatic or cycloaliphatic, carboiwlic acids of the above kind there may'be mentioned, for instance: butylphenoxy-acetic acid, dodecylphe-.

noxy-acetic acid, tetradecylphenoxy-acetig acid,

, iso-octyl phenoxy-acetic acid, perhydrobenzoyl phenoxy-acetic acid, 'iso-octyl-cresoxy-acetic'- acid, iso-octylphenoxy-ethoxyaceflc acid, dior .tri-butylphenoxy-acetic acid, di-isohexylphemoxy-propionic acid, ca'proyl-phenoxy-'propionic 45 acid, iso-octyl-phenoxy-beta-butyrlc acid, (perhydro phthaloyl) naphthoxy acetic acid, dodecyl-naphthoxy-propionic acid. Examples of the aliphatic and isocyclic nitrogeneous sulfonic acids or sulfuric acid esters are: amino-methane- 50 su1fonlc acid, taurine, methyltaurine, -butylby causinga carboxylic acid of I wherein R: stands for a member selected from stands for a member of the group consisting oftaurine isoheptyltaurine, alpha-ethylhexyltaurine beta-methylaminodiethylether-beta-sul fonicv acid (CHaNlLCI-Ia.CH2.O.CH.CH:.SO3H), dodecyltaurine gamma-aminopropane 9 alphabenzylaminesulfonic acid, sulfanilic acid,metani-,

sulfonic acid, phenyltaurlne, cyclohexyltaurine,

lic acid, aminoethanol sulfuric acid ester, 1.4-

naphthylamine-sulfonic acid.

The reaction of the carboxylic acid anhydrides or chlorides'of high molecular weight with the ,nitrogeneous sulfonic acids or sulfuric acid esters maybe performed in most case'sin an aqueous alkaline solution by the Schotten-Baumann method. The reaction may, however, also be carried out in'the presence of pyridine or another organic base. I Q

According to known methods the free sulfonic acids or sulfuric acid esters maybe prepared from the reaction products thus obtained.

Insofar as the condensation products have a be prepared by transforming a carhoxylic acid of the formula A.O.R'1.COOH or a'chloride thereof amide and converting it'by means of the free hysulfuric acid ester-likeconstitution they may also with a hydroxyamine into the carboxylic acid droxyl group in known manner into a sulfuric acid ester and, if desired, subsequently into a salt of the ester. o

Furthermore, we have found that condensation products from the carboxylic acids of the formula A.O.R1.COOH as above, defined and aminomethanesulfonic .acid may also be prepared by causing formaldehyde and sodium bisuiflte to react at an elevated temperature with amides of the carboxylic acids, Thus, sodium salts of the carboxylic amides of amino-methanesulfonicacid are'obtained. J

The products "may be used as free sulfonic acids or sulfuric acid esters or in the form of their al- 40 E111 salts inclusive the ammonium salts and amine salts.- The water-soluble salts of the amides may beused as capillary agents in the leather or paper-making industry. For instance, the sodium or potassium salts may be applied as wetting-, bucking fulling or washing agents, as washing agents for W001 as well as agents for washing flne laundry goods; furthermore, as a hair wash. The products are distinguished by a. good foaming and a very good cleansing action.

various/industries, for instance, in the textile,

Some of the products may also be used as auxiliary agents in the dyeing industry, i'or'the production of even dyeings penetrating through the goods, as dispersing agents for dyestufls, instead of soaps for soaping dyeings. The products may be used either as such or in admixture with other known textile adjuvants, for instance, Turkey red oil, .alkylated naphthalenesulfonic acids or the products known in the art as fatty acid condensation products or .fatty alcohol sultonates.

The products may also be mixed with other additions, for instance, organic solvents, such asbenzyl alcohol, chlorinated hydrocarbons, monoglycol ethers, cyclohexanol, yielding oxygen, such as sodium perborate, per? pyrophosphate, stabilizers, such as a magnesium salt, other inorganic salts, such as trisodium phosphate, sodium'pyrophosphate. sodiumhex- The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts are by weight:

1. 282 parts of para-iso-octylphenoxy-acetic acid chloride of the formula:

CH: ,CH: CHa--CHrQO-CHPCOCI prepared by causing 'para-iso-octylphenoxyacetic acid to react with phosphorus trichloride or thionyl chloride, are run into 1480 parts of methyltaurine-sodium salt solution of 12 per cent strength at about 35-40" C., care being taken by simultaneous .addition of caustic soda solution of 32 per cent strength that the mixture shows permanently a distinctly alkaline reaction. Thereupon, it is stirred for 2 hours at 50-55 C., the excess of caustic soda solution is neutralized by adding dilute sulfuric acid and the whole is evaporated to dryness on the waterbath. It is of advantage to extract the last traces v cresoxy-acetic acid chlorides (prepared by condensation of technical olefine mixtures, consisting in the main part of isomeric tetradecylenes, with cresoxy-acetic acids and transformation of the tetradecylcresoxy-acetic acids obtained to the corresponding chlorides), are runinto 1080 parts of a taurine-sodium salt solution of 15 per cent strength, while well stirring, the tempera.- ture of the mixture being maintained at about 35 C. to 40 C. and the reaction of the mixture permanently being kept distinctly alkaline by simultaneous addition of caustic soda solution of 230 per cent strength. Thereupon the reaction is finished by stirring for 2 hours at- 55 C. to 60 C. and the whole is rendered neutral by adding dilute sulfuric acid. The mixture is concentrated to 1400 parts and in this manner a tough, nearly colorless paste of the sodium salts of'isomeric tetradecylcresoxy-acetic acid taurides with a content of 35 per cent is obtained. The cleansing,

effect of the aqueous solutions of the paste even substancesv surpasses that oi! the product obtained as described in Example 1.

3. 332 parts of dibutyl-naphthoxy-acetic acid chloride prepared from dibutylnaphthoxy-acetic acid by reaction with P013 or. thionyl chloride, are at 20 C. ,to 25 C. run into a mixture of 1080 parts of a tau-rine-sodium salt solution of 15 per cent strength with 160 parts of caustic soda solution of 32 per cent strength, with mixture is vigorously agitated by a quickly moving stirrer; the mass is stirred for about 6 to 8 hours at the said temperature. At the end, the excess ofv alkali which may perhaps be present is neutralized by addition of dilute sulfuric acid and the mixture is evaporated to 1265 parts. There is obtained a nearly colorless paste of 35 per cent of the sodium salt of dibutylnaphthoxy-acetic acid tauride. The product possesses properties similar to those named in the foregoing examples.

4. Into 2230. parts of solution of 10 per cent strength of a butyltaurine-sodium salt there are simultaneously run, while well stirring, 140 parts of caustic soda solution of 32 per cent strength and 236 parts of para-cyclohexylphenoxy-acetic acid chloride in such a manner that during the reaction a distinctly alkaline reaction is permanently maintained and the temperature of the mass is about C. to C. Thereupon the whole is allowed'to react for 2 to 3 hours and any excess of alkali which may be present is neutralized by means of dilute sulfuric acid. By evaporating the reaction mass there is obtained a nearly colorless solid mass which may be triturated to a voluminous powder which is easily soluble in water.

5. Into a solution of 10 per cent strength of 210 parts of the sodium salt of meta-aminobenzene sulfonic acid in water there are introduced simultaneously 140 partso'i caustic soda solution of 32 per cent strength and 232 parts of para-isobutylcyclohexyloxy-acetic acid chloride CHI CHr-AIGO-Clir-COCI in such a way that the mass shows permanently a distinctly alkaline reaction and the temperature is maintained at about C. to C.' After neutralization of the excess of alkali which may be present the mass is evaporated to dryness and pulverised. The sodium salt of a sulfonic acid of the following formula CH: CHr-JJ is obtained. The product is easily soluble in water.

6. 274 parts of benzylphenoxypropionic acid chloride are run into 1260 parts of a solution of 12 per cent strength of the sodium salt of the acid sulfuric acid esterot ethanolamine at 15 C. to 20 C. and such a quantity of caustic soda solution of .20 per cent strength is added that the mass shows permanently aieebiy alkaline retill 260. CH'EMlSTRY. CAR

ma mas.

action. The whole is stirred for 2 to 3 hours at 20 C. and rendered neutral by means of dilute sulfuric acid. By evaporating in a vacuum to 1140 epfirts there is obtained the sodium salt of the acid sulfuric acid ester of benzylphenoxypropionic acid ethanolamide in the form of a nearly colorless aqueous paste of 35 per cent strength.

The same product is obtained if benzylphenoxypropionic acid is heated with the equivalent amount of ethanolamine at 180 C. to 190 C., advantageously under reduced pressure, thus transforming it into the ethanolamide, and causing the latter to react with sulfuric acid, for instance according to the following prescription:

300 parts of benzylphenoxypropionic acid ethanolamide are dissolved in 500 parts of diethyl ether and a solution of 174 parts of chlorosulfonic acid in 200 parts of diethyl ether are slowly added thereto at about 10 C. to 15 C. When the sulfonation is finished the whole is stirred at about 15 C.; a stream of dry air being passed through the mass in order to eliminate the dissolved hydrochloric acid. 300 parts of finely ground ice are then added to the mixture and the whole is neutralized at 15 C. to 20 C. with caustic soda solution of 32 per cent strength. When the mass shows an alkaline reaction to litmus paper, the diethyl ether is distilled and the product is made up to 1140 parts by addition of water. The paste of 35 per cent strength thus obtained corresponds in its properties with the product above-described.

7. 2'70 parts of para-caproylphenoxyacetic acid chloride omacoO-oom-oom are run at 30 C. to 40 C. into 1500 parts of a solution of 12 per cent strength of the sodium salt of methyltaurine, such a quantity of caustic soda solution of 32 per cent strength being simul-- taneously introduced, that the reaction is permanently alkaline. The reaction is further stirred for 2 hours at 50 C. to 60 C., the excess of caustic soda solution is neutralized by means of dilute sulfuric acid and the whole is evaporated to dryness on the water bath. After drying for a prolonged time in a vacuum steam vessel a hard mass is obtained which may be ground to form a powder. The sodium para-caproylphenoxyacetic acid methyl tauride possesses a good foaming effect and a very good washing powder for soiled textile materials.

8. 365 parts of dodecylphenoxyacetic acid ethanolamide, prepared in known manner from dodecylphenoxyacetic acid chloride by reaction with aminoethanol according to the Schotten- Baumann method or by heating the free acid at C. to C. with aminoethanol until the quantitative amount of water i is been split oil, are dissolved in 700 cc. of diethvlether and at 5 C. to 10 C. 125 parts of chloro-sulfonic acid are gradually added, while stirring. The whole is stirred for 2 hours at 15 C., the still dissolved hydrochloric acid is removed by a dry stream of air, 400 parts of ground ice are added and the whole is neutralized by means of caustic soda. solution of 32 per cent strength. The diethyl ether is distilled at a feebly alkaline reaction and the product corresponding to a quantitative yield of 467 grams of sulfuric acid ester of 100 per cent is made up by addition of water to a colorless SEARCH R00 paste containing 30 per cent of substance=1330 grams of paste. The product foams very well in an aqueous dilution and shows a strong washing and cleansing effect.

9. 282 parts of iso-octylphenoxyacetic acid chloride are run at 30 C. to 40 C. into 1100 parts of a solution of 13 per cent strength of sodium aminoethane sulfonate; such a quantity of caustic soda solution of 32 per cent strength is simultaneously added that a distinctly alkaline reaction is permanently maintained. After stirring for further 2 to 3 hours at 50 C., the pastelike reaction mass is neutralised by means of dilute sulfuric acid and the whole is evaporated to dryness. The aqueous solution of the sodium salt of iso-octylphenoxy-acetic acid aminoethylsulfonic acid shows a good cleansing effect and foams very well.

The same product is obtained by causing isooctylphenoxyacetic acid amide to react in known manner with formaldehyde and sodium bisulflte.

We claim:

1. The process of manufacturing acid amides which comprises reacting a compound selected from the group consisting of compounds having one of the general formulae:

A.O.Ri.CO

0 and A.O.R .0OCl

A.O.R1.CO

wherein A stands for a member of the group consisting of aromatic and hydroaromatic hydrocarbon radicals substituted in the nucleus at least once by a hydrocarbon radical of at least 4 C-atoms, R1 stands for a member of the group consisting of aliphatic hydrocarbon radicals and allphatic hydrocarbon radicals whose carbon chain is interrupted by O, with a compound of the general formula:

N-RaY wherein R2 stands for a member of the group consisting of aliphatic hydrocarbon radicals, aliphatic hydrocarbon radicals whose carbon chain is interrupted by O, cycloaliphatic, aliphatic-aromatic and aromatic hydrocarbon radicals, R3 stands for a member selected from the group consisting of hydrogen and aliphatic, cycloaliphatic, aliphaticaromatic and aromatic hydrocarbon radicals, Y stands for a member of the group consisting of OSO3Me and SOaMe, Me being a member of the group consisting of alkali metals, NH4 and the radical NH4 in which at least one H-atom and at most three H-atoms are substituted.

2. The products of the general formula:

/Ra A.O.Rl.CO.N

RzY

wherein A stands for a member of the group consisting of aromatic and hydroaromatic hydrocarbon radicals substituted in the nucleus at least once by a hydrocarbon radical of at least 4 C-atoms, R1 stands for a. member of the group consisting of aliphatic hydrocarbon radicals and aliphatic hydrocarbon radicals whose carbon chain is interrupted by 0, R: stands for a member of the groug consisting of aliphatic hydrocarbon radicals, aliphatic hydrocarbon radicals whose carbon chain is interrupted by O, cycloaliphatic, aliphatic-aromatic and aromatic hydrocarbon radicals, R3 stands for a member selected from the group consisting of hydrogen and aliphatic, cycloaliphatic, aliphatic-aromatic and aromatic hydrocarbon radicals, and Y stands for a member of the group consisting of OSOsZ and SOoZ, Z being a member of the group consisting of hydrogen, alkali metals, N114 and the radical NE; in which at least one H-atom and at most three H- atoms are substituted.

3. The product of the formula:

4. The product of the formula:

5. The product of the formula: 10

on: on:

CH: Ha

KARL HORST. 15 HEmz scrum). 

